US5863344A - Cleaning solutions for semiconductor devices - Google Patents
Cleaning solutions for semiconductor devices Download PDFInfo
- Publication number
- US5863344A US5863344A US08/766,809 US76680996A US5863344A US 5863344 A US5863344 A US 5863344A US 76680996 A US76680996 A US 76680996A US 5863344 A US5863344 A US 5863344A
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- United States
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- semiconductor devices
- cleaning
- cleaning solution
- cleaning solutions
- ammonium hydroxide
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- Expired - Lifetime
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- H10P70/234—
Definitions
- the present invention relates to solutions useful for cleaning semiconductor devices. More particularly, the invention relates to solutions useful for cleaning impurities from semiconductor devices produced as by-products during the formation of metal wiring layers.
- impurities include, for example, metals, polymers, and particles.
- the impurities often adversely affect the yield and reliability of products containing the semiconductor devices. Accordingly, cleaning the semiconductor devices has become increasingly important in semiconductor manufacturing processes.
- aluminum is generally used as a wiring material and serves to connect the devices.
- the deposited aluminum often reacts with the underlying silicon layer.
- the junction between the aluminum and the silicon is typically destroyed due primarily to the presence of a spike at their contact surface. As a result, the semiconductor device often experiences failure.
- aluminum alloys containing a predetermined amount of copper, silicon, and the like are used as a wiring material. Subsequent to etching such an aluminum alloy layer, the aluminum is usually removed by an etch solution. The copper and silicon typically remain however, and may react with components of the etch solution. As a result, impurities are often produced.
- a metal layer may be etched using a conventional etch gas and a photoresist pattern.
- polymer contaminants are often produced by a reaction between the etch gas, the photoresist, and the metal layer. Since the presence of the polymer contaminants may greatly increase contact resistance between metal patterns, it is typically necessary to remove the polymer contaminants by applying a cleaning solution.
- Conventional cleaning solutions typically contain an amine compound such as aminoethyl piperidine, isopropylamine, hydroxyethyl morpholine, aminoalcohol, and diethylenetriamine; and a solvent such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, and N, N-dimethylformamide.
- the cleaning solutions comprise tetramethyl ammonium hydroxide, acetic acid, and water.
- deionized water is used in the cleaning solutions.
- the cleaning solution components may be used in various amounts.
- the concentration of the acetic acid is at least 99.9 percent based on the weight of the cleaning solution.
- the concentration of the tetramethyl ammonium hydroxide ranges from about 1 to about 30 percent based on the weight of the cleaning solution.
- the components may also be employed in various volume ratios.
- the volume ratio of acetic acid to tetramethyl ammonium hydroxide may range from about 1 to about 50.
- the volume ratio of water to tetraethyl ammonium hydroxide may range from about 1 to about 50.
- the invention also provides methods for removing impurities from semiconductor devices.
- the methods comprise treating the semiconductor devices with the above cleaning solutions to remove impurities from the semiconductor devices.
- FIG. 1 is a graph illustrating particle removing rate versus frequency of cleaning operations using cleaning solutions of the present invention
- FIGS. 2A and 2B are SEM photographs illustrating side and front views of a via hole contaminated by polymer contaminants before cleaning
- FIGS. 2C and 2D are SEM photographs illustrating side and front views of a via hole after polymer contaminants are removed using the cleaning solutions of the present invention
- FIG. 3A is an SEM photograph illustrating a profile of a metal layer obtained by a destructive method prior to being cleaned
- FIG. 3B is an SEM photograph illustrating a profile of a metal layer obtained by a destructive method after being cleaned with the cleaning solutions of the present invention
- FIG. 3C is an SEM photograph illustrating a profile of a metal layer obtained by a non-destructive method prior to being cleaned.
- FIG. 3D is an SEM photograph illustrating a profile of a metal layer obtained by a non-destructive method after being cleaned with the cleaning solutions of the present invention.
- the present invention relates to cleaning solutions for semiconductor devices.
- the cleaning solutions comprise tetramethyl ammonium hydroxide, acetic acid, and water.
- Deionized water is preferably used for the purposes of the invention. It is also preferred that the cleaning solutions include solutions of tetramethyl ammonium hydroxide.
- the components in the cleaning solutions may be used in various amounts.
- the concentrations of acetic acid may be at least about 99.9 percent based on the weights of the cleaning solutions.
- concentrations of tetramethyl ammonium hydroxide can range from about 1 to about 30 percent based on the weights of the cleaning solutions.
- the volume ratios of acetic acid to tetramethyl ammonium hydroxide preferably range from about 1 to about 50.
- the volume ratios of water to tetramethyl ammonium hydroxide preferably range from about 1 to about 50.
- the invention also relates to methods for removing impurities from semiconductor devices.
- the methods include contacting the semiconductor devices with the cleaning solutions to remove the impurities from the semiconductor devices.
- the cleaning solutions include those described herein.
- impurities is to be broadly construed and includes, but is not limited to, particles which result from the formation of metal wiring layers on the semiconductor devices, polymer contaminants produced as a result of etching metal layers in semiconductor devices, and the like.
- the cleaning solution of the present invention In order to estimate the particle removing effect of the cleaning solution of the present invention, at least 1000 particles were artificially produced on a semiconductor substrate.
- the semiconductor substrate was then submerged into a cleaning solution which contained 2.38 weight percent of tetramethyl ammonium hydroxide solution, acetic acid, and deionized water.
- the substrate was treated for a predetermined time, and was then examined by a surfscan sold by the Tencor Co.
- FIG. 1 is a graph showing the particle removing rate according to the frequency of cleaning operations using the above cleaning solution. As shown, the cleaning solution advantageously removes a large percentage of the particles present on the semiconductor substrate.
- a semiconductor substrate containing polymer contaminants was submerged into a cleaning solution, cleaned for a predetermined period of time, and then examined by an SEM.
- FIGS. 2A-2D are SEM photos showing the effects of the cleaning solution of the present invention on cleaning a via hole contaminated with the polymer contaminants. Specifically, FIGS. 2A and 2B illustrate side and front views of the via hole respectively which is contaminated with the polymer contaminants prior to cleaning, while FIGS. 2C and 2D illustrate side and front views of the via hole respectively after cleaning using a cleaning solution of the present invention. As shown in the figures, the cleaning solution of the present invention effectively removed the polymer contaminants from the semiconductor substrate.
- FIG. 3A is an SEM photo showing a profile of an uncleaned metal layer obtained by a destructive method.
- FIG. 3B is an SEM photo showing a profile of the metal layer after being cleaned with a cleaning solution of the present invention. As can be seen, the cleaning solution effectively cleans the metal layer with minimal damage.
- FIG. 3C is an SEM photo showing a profile of an uncleaned metal layer obtained by a non-destructive method.
- FIG. 3D is an SEM photo showing a profile of the metal layer after being cleaned with a cleaning solution of the present invention. As can be seen, the cleaning solution effectively cleans the metal layer with minimal damage.
- the cleaning solutions of the invention are highly advantageous. Impurities such as particles and polymer contaminants resulting from the formation of a metal wiring layer can be effectively removed without significant damage to the metal layer. As a result, a semiconductor device containing the metal layer is more reliable. Additionally, wiring shorts are reduced.
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- Cleaning Or Drying Semiconductors (AREA)
- Weting (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR199552704 | 1995-12-20 | ||
| KR1019950052704A KR100360394B1 (en) | 1995-12-20 | 1995-12-20 | Cleaning method of semiconductor substrate and cleaning liquid used for it |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5863344A true US5863344A (en) | 1999-01-26 |
Family
ID=19441873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/766,809 Expired - Lifetime US5863344A (en) | 1995-12-20 | 1996-12-13 | Cleaning solutions for semiconductor devices |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US5863344A (en) |
| JP (1) | JPH09181028A (en) |
| KR (1) | KR100360394B1 (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6194366B1 (en) | 1999-11-16 | 2001-02-27 | Esc, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
| US6232246B1 (en) * | 1998-03-18 | 2001-05-15 | Sony Corporation | Method of fabricating semiconductor device |
| US6541391B2 (en) | 2001-02-28 | 2003-04-01 | Micron Technology, Inc. | Methods of cleaning surfaces of copper-containing materials, and methods of forming openings to copper-containing substrates |
| US20030077903A1 (en) * | 2001-10-24 | 2003-04-24 | Andreas Michael T. | Copper post-etch cleaning process |
| US6610599B1 (en) * | 2002-06-19 | 2003-08-26 | Lucent Technologies Inc. | Removal of metal veils from via holes |
| US6653243B2 (en) * | 2000-05-25 | 2003-11-25 | Micron Technology, Inc. | Methods of cleaning surfaces of copper-containing materials, and methods of forming openings to copper-containing substrates |
| US6723691B2 (en) | 1999-11-16 | 2004-04-20 | Advanced Technology Materials, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
| US6878213B1 (en) * | 1998-12-07 | 2005-04-12 | Scp Global Technologies, Inc. | Process and system for rinsing of semiconductor substrates |
| US20060148666A1 (en) * | 2004-12-30 | 2006-07-06 | Advanced Technology Materials Inc. | Aqueous cleaner with low metal etch rate |
| US20060166847A1 (en) * | 2005-01-27 | 2006-07-27 | Advanced Technology Materials, Inc. | Compositions for processing of semiconductor substrates |
| US20060229221A1 (en) * | 2005-03-30 | 2006-10-12 | Advanced Technology Materials Inc. | Aqueous cleaner with low metal etch rate |
| US20070037720A1 (en) * | 2001-06-20 | 2007-02-15 | Cornell Research Foundation, Inc. | Removable marking system |
| US20070173062A1 (en) * | 2006-01-23 | 2007-07-26 | Micron Technology, Inc. | Method of cleaning a surface of a cobalt-containing material, method of forming an opening to a cobalt-containing material, semiconductor processing method of forming an integrated circuit comprising a copper-containing conductive line, and a cobalt-containing film cleaning solution |
| US20080076688A1 (en) * | 2006-09-21 | 2008-03-27 | Barnes Jeffrey A | Copper passivating post-chemical mechanical polishing cleaning composition and method of use |
| US20090036343A1 (en) * | 2007-08-03 | 2009-02-05 | Epoch Material Co., Ltd. | Aqueous Cleaning Composition For Semiconductor Copper Processing |
| US20090120457A1 (en) * | 2007-11-09 | 2009-05-14 | Surface Chemistry Discoveries, Inc. | Compositions and method for removing coatings and preparation of surfaces for use in metal finishing, and manufacturing of electronic and microelectronic devices |
| US20100056409A1 (en) * | 2005-01-27 | 2010-03-04 | Elizabeth Walker | Compositions for processing of semiconductor substrates |
| EP2348142A1 (en) | 2010-01-25 | 2011-07-27 | Dominion Engineering, Inc. | Method and composition for removing scale deposits formed on a metal surface within a steam generating system |
| US9528078B2 (en) | 2006-09-21 | 2016-12-27 | Advanced Technology Materials, Inc. | Antioxidants for post-CMP cleaning formulations |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997049844A1 (en) * | 1996-06-27 | 1997-12-31 | Toyo Tanso Co., Ltd. | Crucible for crystal pulling and method of manufacturing same |
| JP3039493B2 (en) * | 1997-11-28 | 2000-05-08 | 日本電気株式会社 | Substrate cleaning method and cleaning solution |
| KR100660344B1 (en) * | 2005-06-22 | 2006-12-22 | 동부일렉트로닉스 주식회사 | Metal wiring formation method of semiconductor device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039371A (en) * | 1975-09-18 | 1977-08-02 | International Business Machines Corporation | Etchant for polyimides |
| SU975831A1 (en) * | 1981-03-05 | 1982-11-23 | V Elektrotech I V I Lenina | Solution for cleaning surfaces of molybdenium parts |
| US5320707A (en) * | 1989-02-27 | 1994-06-14 | Hitachi, Ltd. | Dry etching method |
| JPH06275723A (en) * | 1993-03-23 | 1994-09-30 | Sanyo Electric Co Ltd | Manufacture of semiconductor device |
| US5466389A (en) * | 1994-04-20 | 1995-11-14 | J. T. Baker Inc. | PH adjusted nonionic surfactant-containing alkaline cleaner composition for cleaning microelectronics substrates |
| US5595927A (en) * | 1995-03-17 | 1997-01-21 | Taiwan Semiconductor Manufacturing Company Ltd. | Method for making self-aligned source/drain mask ROM memory cell using trench etched channel |
-
1995
- 1995-12-20 KR KR1019950052704A patent/KR100360394B1/en not_active Expired - Fee Related
-
1996
- 1996-12-13 US US08/766,809 patent/US5863344A/en not_active Expired - Lifetime
- 1996-12-19 JP JP8354566A patent/JPH09181028A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039371A (en) * | 1975-09-18 | 1977-08-02 | International Business Machines Corporation | Etchant for polyimides |
| SU975831A1 (en) * | 1981-03-05 | 1982-11-23 | V Elektrotech I V I Lenina | Solution for cleaning surfaces of molybdenium parts |
| US5320707A (en) * | 1989-02-27 | 1994-06-14 | Hitachi, Ltd. | Dry etching method |
| JPH06275723A (en) * | 1993-03-23 | 1994-09-30 | Sanyo Electric Co Ltd | Manufacture of semiconductor device |
| US5466389A (en) * | 1994-04-20 | 1995-11-14 | J. T. Baker Inc. | PH adjusted nonionic surfactant-containing alkaline cleaner composition for cleaning microelectronics substrates |
| US5595927A (en) * | 1995-03-17 | 1997-01-21 | Taiwan Semiconductor Manufacturing Company Ltd. | Method for making self-aligned source/drain mask ROM memory cell using trench etched channel |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6232246B1 (en) * | 1998-03-18 | 2001-05-15 | Sony Corporation | Method of fabricating semiconductor device |
| US6878213B1 (en) * | 1998-12-07 | 2005-04-12 | Scp Global Technologies, Inc. | Process and system for rinsing of semiconductor substrates |
| US6194366B1 (en) | 1999-11-16 | 2001-02-27 | Esc, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
| US6723691B2 (en) | 1999-11-16 | 2004-04-20 | Advanced Technology Materials, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
| US20050215064A1 (en) * | 2000-05-25 | 2005-09-29 | Morgan Paul A | Methods of cleaning surfaces of copper-containing materials, and methods of forming openings to copper-containing substrates |
| US7060631B2 (en) | 2000-05-25 | 2006-06-13 | Micron Technology, Inc. | Methods of cleaning surfaces of copper-containing materials, and methods of forming openings to copper-containing substrates |
| US6653243B2 (en) * | 2000-05-25 | 2003-11-25 | Micron Technology, Inc. | Methods of cleaning surfaces of copper-containing materials, and methods of forming openings to copper-containing substrates |
| US20040110372A1 (en) * | 2000-05-25 | 2004-06-10 | Morgan Paul A. | Methods of cleaning surfaces of copper-containing materials, and methods of forming openings to copper-containing substrates |
| US6955995B2 (en) | 2000-05-25 | 2005-10-18 | Mircon Technology, Inc. | Methods of cleaning surfaces of copper-containing materials, and methods of forming openings to copper-containing substrates |
| US6541391B2 (en) | 2001-02-28 | 2003-04-01 | Micron Technology, Inc. | Methods of cleaning surfaces of copper-containing materials, and methods of forming openings to copper-containing substrates |
| US20070037720A1 (en) * | 2001-06-20 | 2007-02-15 | Cornell Research Foundation, Inc. | Removable marking system |
| US20030077903A1 (en) * | 2001-10-24 | 2003-04-24 | Andreas Michael T. | Copper post-etch cleaning process |
| US6835668B2 (en) | 2001-10-24 | 2004-12-28 | Micron Technology, Inc. | Copper post-etch cleaning process |
| US6589882B2 (en) | 2001-10-24 | 2003-07-08 | Micron Technology, Inc. | Copper post-etch cleaning process |
| US6610599B1 (en) * | 2002-06-19 | 2003-08-26 | Lucent Technologies Inc. | Removal of metal veils from via holes |
| US20060148666A1 (en) * | 2004-12-30 | 2006-07-06 | Advanced Technology Materials Inc. | Aqueous cleaner with low metal etch rate |
| US20060166847A1 (en) * | 2005-01-27 | 2006-07-27 | Advanced Technology Materials, Inc. | Compositions for processing of semiconductor substrates |
| US20100056409A1 (en) * | 2005-01-27 | 2010-03-04 | Elizabeth Walker | Compositions for processing of semiconductor substrates |
| US7922823B2 (en) | 2005-01-27 | 2011-04-12 | Advanced Technology Materials, Inc. | Compositions for processing of semiconductor substrates |
| US7923423B2 (en) | 2005-01-27 | 2011-04-12 | Advanced Technology Materials, Inc. | Compositions for processing of semiconductor substrates |
| US20060229221A1 (en) * | 2005-03-30 | 2006-10-12 | Advanced Technology Materials Inc. | Aqueous cleaner with low metal etch rate |
| US7365045B2 (en) | 2005-03-30 | 2008-04-29 | Advanced Tehnology Materials, Inc. | Aqueous cleaner with low metal etch rate comprising alkanolamine and tetraalkylammonium hydroxide |
| US7367343B2 (en) | 2006-01-23 | 2008-05-06 | Micron Technology, Inc. | Method of cleaning a surface of a cobalt-containing material, method of forming an opening to a cobalt-containing material, semiconductor processing method of forming an integrated circuit comprising a copper-containing conductive line, and a cobalt-containing film cleaning solution |
| US20080176405A1 (en) * | 2006-01-23 | 2008-07-24 | Andreas Michael T | Method of cleaning a surface of a cobalt-containing material, method of forming an opening to a cobalt-containing material, semiconductor processing method of forming an integrated circuit comprising a copper-containing conductive line, and a cobalt-containing film cleaning solution |
| US20070173062A1 (en) * | 2006-01-23 | 2007-07-26 | Micron Technology, Inc. | Method of cleaning a surface of a cobalt-containing material, method of forming an opening to a cobalt-containing material, semiconductor processing method of forming an integrated circuit comprising a copper-containing conductive line, and a cobalt-containing film cleaning solution |
| US7964109B2 (en) | 2006-01-23 | 2011-06-21 | Micron Technology, Inc. | Method of cleaning a surface of a cobalt-containing material, method of forming an opening to a cobalt-containing material, semiconductor processing method of forming an integrated circuit comprising a copper-containing conductive line, and a cobalt-containing film cleaning solution |
| US20080076688A1 (en) * | 2006-09-21 | 2008-03-27 | Barnes Jeffrey A | Copper passivating post-chemical mechanical polishing cleaning composition and method of use |
| US9528078B2 (en) | 2006-09-21 | 2016-12-27 | Advanced Technology Materials, Inc. | Antioxidants for post-CMP cleaning formulations |
| USRE46427E1 (en) * | 2006-09-21 | 2017-06-06 | Entegris, Inc. | Antioxidants for post-CMP cleaning formulations |
| US20090036343A1 (en) * | 2007-08-03 | 2009-02-05 | Epoch Material Co., Ltd. | Aqueous Cleaning Composition For Semiconductor Copper Processing |
| US8067352B2 (en) | 2007-08-03 | 2011-11-29 | Epoch Material Co., Ltd. | Aqueous cleaning composition for semiconductor copper processing |
| US20090120457A1 (en) * | 2007-11-09 | 2009-05-14 | Surface Chemistry Discoveries, Inc. | Compositions and method for removing coatings and preparation of surfaces for use in metal finishing, and manufacturing of electronic and microelectronic devices |
| EP2348142A1 (en) | 2010-01-25 | 2011-07-27 | Dominion Engineering, Inc. | Method and composition for removing scale deposits formed on a metal surface within a steam generating system |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09181028A (en) | 1997-07-11 |
| KR100360394B1 (en) | 2003-01-24 |
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